Aqueous Cross-linking Compositions and Methods

ABSTRACT

Water-borne cross-linking polymeric compositions and related embodiments, such as methods of making and using the compositions, as well as products formed with said compositions are described. The water-borne composition may comprise one or more polymers formulated from one or more monomers of which at least one is a monomer that yields acetaldehyde as a hydrolysis product, and incorporating cross-linking functionality such as, but not limited to, carbonyl or epoxy functionality, and a blocked cross-linking agent, for example, a hydrazone. Neither the cross-linking functionality nor the acetaldehyde reacts with the blocked cross-linking agent; however, the blocked cross-linking agent is capable of conversion to an alternative form cross-linking agent such as, but not limited to, a hydrazide, to yield a cross-linked polymer. The alternative form cross-linking agent may be formed in an equilibrium reaction including the blocked cross-linking agent.

CROSS-REFERENCE TO RELATED APPLICATION

This application claims the benefit of U.S. Provisional Patent Application No. 61/597,571 filed Feb. 10, 2012, and further is a continuation-in-part and claims the benefit of United States Non-Provisional patent application Ser. No. 13/152,856, filed Jun. 3, 2011. This application further claims the benefit, through said application Ser. No. 13/152,856, of U.S. Provisional Patent Application Ser. No. 61/351,657, filed Jun. 4, 2010. The above-mentioned applications are incorporated herein by reference, each in its entirety as if fully set forth below.

FIELD OF THE INVENTION

The invention concerns water-borne cross-linking polymeric compositions and related embodiments, such as methods of making and using the compositions, as well as products formed with said compositions.

BACKGROUND

Water-borne paints, primers, coatings, inks, adhesives, and other water-borne film-forming compositions (“water-borne compositions”) may comprise solvents, binder, pigments and other additional components that favorably affect various properties of the compositions, such as polymeric surfactants and dispersants. The binder and the pigment, if present, are the primary solid components of the water-borne composition and remain on surfaces to which they have been applied forming a solid layer as solvent evaporates. In water-borne compositions, the primary solvent is water. Typical water-borne compositions include latex paints.

Polymer latexes or dispersions are widely used in water-based coatings. The polymer latex or dispersion is dried to form a film via coalescence to obtain desired mechanical and physical properties. Coalescence is a process whereby polymer particles in aqueous dispersion come into contact with one another during drying, and polymer chains form (i.e., diffuse) across boundaries of latex/dispersion particles to yield continuous films with good bonding of the particles.

A method of improving the properties of films formed by water-borne compositions is to include polymers that are capable of cross-linking. The polymers may be self cross-linking or dependent on the involvement of a cross-linking agent to react with the polymers.

Of the aforementioned polymers, those that are self-cross-linking containing components such as acetoacetoxyethylmethacrylate (“AAEM”), glycidal methacrylate, and oxidative or UV curable functional groups are typically used in (among other things) water-borne coatings, inks, and adhesives. Unfortunately, self-cross-linked polymers yield only minimally improved mechanical properties in the resultant films, particularly for scrubability of water-borne paints. On the other hand, cross-linked polymers formed with the involvement of a cross-linking agent have the potential for exhibiting superior performance.

That is to say, cross-linking technology based on the use of a cross-linking agent to cross-link binders and/or other polymeric additives such as polymeric surfactants and dispersants (U.S. Pat. No. 5,348,997) or rheology modifiers (U.S. Published Patent Application No. 2009/0162669) is comparatively attractive because it affords the possibility of realizing one or more property improvements of a substantial and commercially significant nature. To with, cross-linking of polymers in coatings, inks, and other water-borne film-forming compositions can improve physical and mechanical strength, adhesion, and durability. In coating applications, cross-linking may also improve scrubability, blocking resistance, chemical resistance, and weatherability (see U.S. Pat. No. 7,547,740 and U.S. Patent Application Publication No. 2007/0265391). Cross-linking of polymer constituents may also enhance adhesion and bonding strength for adhesives. Additionally, cross-linking is widely utilized in the formulation of printing inks, in order to improve the mechanical and chemical resistance of prints.

Accordingly, it is to be understood that cross-linking during and after coalescence with a cross-linking agent further enhances the physical and mechanical properties of the films. However, if the polymer cross-linking reaction begins before the water-borne composition is applied to a surface, the resultant film may have poor physical and mechanical properties. Premature cross-linking is that which occurs within the polymer latex or dispersion, such as a latex or dispersion of a polymer which has carbonyl and/or epoxy functionality, before it is applied to a surface. It may prevent coatings from forming coalesced films.

Premature cross-linking in compositions used for paints, inks, adhesives, dispersants, polymeric surfactants or rheology modifiers can also be disadvantageous in causing viscosity instability, thus reducing shelf-life. For example, typical latex base paints are manufactured in bulk and then dispensed into retail containers (such as a can) for shipping and storage. The retail container and its contents may be kept in a warehouse or a retail store prior to sale and ultimate use. During this storage period, cross-linking of the polymers may occur, thereby reducing the quality of the latex paint. The cross-linked polymers may gel and/or build up viscosity in the can and a paint film formed therefrom can have reduced physical and mechanical properties such as reduced scrubability.

For instance, in an effort to improve properties, water-borne compositions have been produced with polymers comprising a monomer such as diacetone acrylamide (“DAAM”) and the cross-linking agent adipic acid dihydrazide (“ADH”). Without significant pre-application cross-linking, such water-borne compositions give improved properties over paint comprising non-cross-linkable polymer, but the improvement is not realized if there is any substantial pre-application cross-linking. Studies have shown that the cross-linking of polymers comprising DAAM with ADH cross-linking agent through a keto-hydrazide reaction has a substantial reaction rate in an aqueous solution. (“The diacetone acrylamide cross-linking reaction and its influence on the film formation of an acrylic latex”, Journal of Coatings Technology and Research, 5(3), 285-297, 2008.) Consequently, premature cross-linking impedes the attainment of desired properties.

An attempt to address the problem of cross-linking prior to application of a polymeric composition containing a polyhydrazide or the like appears in U.S. Pat. No. 4,786,676. There it is taught that polymeric compositions which have a long shelf life in aqueous solutions or dispersions and which undergo cross-linking after drying at room temperature or elevated temperatures are obtainable by reacting polymeric organic compounds possessing carbonyl and carboxyl groups with polyhydrazides in the presence of monoketones and/or monoaldehydes. However, the development discussed in the patent is not adequate for reliably suppressing premature cross-linking because there are side reactions which introduce impurities that degrade the desired stoichiometry, because any chemical species that might prevent premature cross-linking would not be produced in sufficient quantity within a time frame that the undesired reaction could be precluded, and because the use of (at least) ketones can present a safety hazard. It can be seen that the patent's teaching does not afford a practical solution.

Thus, there exists a need for a water-borne composition, comprising a polymer having carbonyl and/or epoxy functionality, with improved physical, chemical and mechanical properties, such as, scrubability. Further, there is a need for a water-borne composition wherein a component cross-linkable polymer does not undergo significant cross-linking prior to application of the composition, especially for water-borne paints. But that is not the full extent of the conventional technology's shortcomings. More specifically, various polymers comprising vinyl-containing monomer units that upon hydrolysis yield acetaldehyde (e.g., vinyl alkyl ester units, especially vinyl acetate units), such as vinyl acetate-acrylic and vinyl acetate-ethylene copolymers, are recognized in the art as being highly advantageous when utilized as the binder in an aqueous latex paint or other coating. However, in our experience it can be even more difficult to elicit satisfactory performance from these specific polymers than previously described. The question arises whether, with such vinyl-containing polymers, there is yet another undesirable phenomenon which must be identified and counteracted in order to realize the substantial performance potential from cross-linked binder materials.

SUMMARY OF THE INVENTION

It is an object of the invention to provide a water-borne composition comprising a cross-linkable polymer having vinyl-containing monomer units which, when applied to a surface, forms a film with good mechanical and physical properties.

It is still another object of the invention to provide a water-borne composition comprising cross-linked polymeric material having vinyl-containing monomer units which, as a component of a film, results in the exhibition of good mechanical and physical properties by the film.

It is another object of the invention to provide a water-borne composition comprising a cross-linkable polymer having vinyl-containing monomer units in which not only is premature cross-linking mitigated, but also other interference with the desired realization of cross-linking.

It is yet another object of the invention to provide methods of making and using the water-borne composition as aforesaid, including a coating or the like exhibiting one or more favorable mechanical or physical properties.

These and other objects of the invention are secured through utilization of an inhibited cross-linking agent that is subject to an equilibrium reaction between one chemical form that is not capable of reacting with the cross-linkable vinyl-containing functionality in film-forming polymers (“blocked cross-linking agent”) and an alternative form that is capable of entering into a cross-linking reaction with such functionality (herein, “cross-linking agent”).

Accordingly, in one aspect the invention is directed to a water-borne polymeric composition, which comprises: water; a polymer comprising one or more carbonyl groups, one or more epoxy groups, or both one or more carbonyl groups and one or more epoxy groups, and which polymer includes vinyl-containing monomer units and has been formed from one or more monomers, at least one of said monomers being a vinyl-containing monomer which yields acetaldehyde as a hydrolysis product; and a blocked cross-linking agent having at least one hydrazone group incorporated therein.

In another aspect the invention is directed to a cross-linked polymeric material, which comprises: a first polymer moiety and a second polymer moiety, at least one of said first and second polymer moieties including vinyl-containing monomer units and having been formed from one or more monomers, at least one of said monomers having been a vinyl-containing monomer which yields acetaldehyde as a hydrolysis product; and cross-linkage formed by reaction of a cross-linking agent with each of the first and second polymer moieties, which agent is derived from a blocked cross-linking agent having at least one hydrazone group incorporated therein, said cross-linkage being between a plurality of sites on the first polymer moiety and their respective corresponding sites on the second polymer moiety via a cross-linking moiety attached at one of said sites on the first polymer moiety and also at the corresponding site on the second polymer moiety; each of the sites on the first and second moieties being one at which there was a carbonyl group or epoxy group prior to cross-linking.

In yet another aspect the invention is directed to a method of preparing a water-borne composition, comprising: combining a blocked cross-linking agent comprising at least one hydrazone group and an aqueous dispersion of one or more cross-linkable polymers, wherein at least one polymer in the dispersion comprises one or more carbonyl groups, one or more epoxy groups, or both one or more carbonyl groups and one or more epoxy groups, which polymer includes vinyl-containing monomer units and has been formed from one or more monomers, at least one of said monomers being a vinyl-containing monomer which yields acetaldehyde as a hydrolysis product.

In a further aspect the invention is directed to a method of making a cross-linked polymeric material, which comprises combining an aqueous dispersion of a first polymer moiety having incorporated therein one or more carbonyl groups, one or more epoxy groups, or both one or more carbonyl groups and one or more epoxy groups and a second polymer chain having incorporated therein one or more carbonyl groups and one or more epoxy groups, or both one or more carbonyl groups and one or more epoxy groups, at least one of said first and second polymer moieties including vinyl-containing monomer units and having been formed from one or more monomers, at least one of said monomers having been a vinyl-containing monomer which yields acetaldehyde as a hydrolysis product; and a blocked cross-linking agent having at least one hydrazone group incorporated therein.

And, in still another aspect the invention is directed to a method of coating a surface, comprising: applying an aqueous polymeric dispersion on a surface, wherein the aqueous polymeric dispersion comprises water, one or more polymers, and a blocked cross-linking agent comprising at least one hydrazone group, wherein at least one of the polymers comprises one or more carbonyl groups, one or more epoxy groups, or both one or more carbonyl groups and one or more epoxy groups, and wherein at least one of said polymers includes vinyl-containing monomer units and has been formed from one or more monomers, at least one of said monomers being a vinyl-containing monomer which yields acetaldehyde as a hydrolysis product; and is correspondingly directed to a coating formed by such method.

In even broader aspects the invention is directed to

(i) a water-borne composition as aforesaid, except that the polymer is one having functionality capable of interacting with a cross-linking agent, which functionality can be (without limitation) carbonyl, epoxy or both, and said blocked cross-linking agent along with said cross-linking agent are such that the blocked cross-linking agent has at least one functional group that is not capable of reacting with said functionality of the polymer but is convertible via an equilibrium reaction to an alternative functional group, thereby to provide the cross-linking agent which is capable of reacting with said functionality;

(ii) a cross-linked polymeric material as aforesaid, except that the first and second polymer moieties have the functionality, and said blocked cross-linking agent as well as said cross-linking agent are, as described in subpart (i) preceding;

(iii) a method of preparing a water-borne composition as aforesaid, except that said at least one polymer has the functionality, and the blocked cross-linking agent as well as the cross-linking agent are, as described in subpart (i) preceding; and

(iv) a method of coating a surface, and a coating formed by such method, as aforesaid, except that said at least one of the polymers has the functionality, and the blocked cross-linking agent as well as the cross-linking agent are, as described in subpart (i) preceding.

As used herein, “polymer” refers to a macromolecule formed by the chemical union of monomers, typically five or more monomers. The term polymer includes homopolymers and copolymers including random copolymers, statistical copolymers, alternating copolymers, gradient copolymers, periodic copolymers, telechelic polymers and polymers of any topology including block copolymers, graft polymers, star polymers, bottle-brush copolymers, comb polymers, branched or hyperbranched polymers, cross-linked polymers and such polymers tethered to particle surfaces or flat surfaces as well as other polymer structures.

The invention confers substantial benefit on its practitioner. A principal advantage flows from the realization that the coincident presence of a hydrazide cross-linking agent (an uninhibited cross-linking agent), and vinyl-containing monomer which yields acetaldehyde as a hydrolysis product, in an aqueous medium, can give rise to threshold interference with the cross-linking reaction. Utilization instead of a counterpart to the cross-linking agent which comprises the hydrazone group (a “blocked” cross-linking agent) in a form convertible to hydrazide at a desired time, prevents the threshold interference. Accordingly, cross-linking is not impeded outright. As a consequence, the additional benefits of blocking a cross-linking agent to restrict cross-linking until the commencement of coalescence or application of the water-borne composition can also be secured. To that end, utilization of a blocked cross-linking agent also mitigates an occurrence of premature cross-linking in the innovative water-borne composition. Therefore, coalescence of polymer solids in a deposit of the composition on a surface is less inhibited by premature cross-linking, and advantageous mechanical or physical properties including adhesion, toughness, water-resistance and scrubability can be attained. Moreover, the presence of substances such as acetone can be eliminated from production operations, thus omitting a source of side reactions and substances which are flammable or volatile. This provides an enhanced level of stoichiometric control and operational safety.

Other aspects and features of embodiments of the present invention will become apparent to those of ordinary skill in the art, upon reviewing the following description of specific, exemplified embodiments. While features of the present invention may be discussed relative to certain embodiments, all embodiments of the present invention can include one or more of the features discussed herein (unless otherwise precluded by the clear meaning of related disclosure). While one or more embodiments may be discussed as having certain advantageous features, one or more of such features may also be used with the various embodiments of the invention discussed herein. In similar fashion, while exemplified embodiments may be discussed below as composition embodiments it is to be understood that such exemplified embodiments can be implemented in various methods as well.

DETAILED DESCRIPTION OF CERTAIN PREFERRED EMBODIMENTS

A central feature of the invention is the suppression (at least in substantial part) of the counter cross-linking effects of bringing together vinyl-containing monomer which yields acetaldehyde as a hydrolysis product, and a cross-linking agent, in an aqueous medium. By this is meant that, in connection with the instant invention, we have observed the special difficulty associated with cross-linking of polymers, especially copolymers (such as vinyl acetate-acrylic and vinyl acetate-ethylene copolymers), formed utilizing monomers at least one of which is a vinyl-containing monomer yielding acetaldehyde as a hydrolysis product, that arises from such monomer's (or monomers') undesirable susceptibility to hydrolysis. Thus, those monomers are highly water-sensitive, and the acetaldehyde hydrolysis product has an active carbonyl group which reacts with hydrazide cross-linking agents such as ADH.

During the “wet stage”, i.e., up through the time when the composition has not yet dried, water is still present which can react with the aforementioned vinyl-containing monomer to form acetaldehyde. The acetaldehyde molecules are smaller than cross-linkable groups such as DAAM, and copolymers or monomers containing any such group. It turns out that those acetaldehyde molecules, having more mobility, are more likely to find cross-linking molecules like ADH. In this manner, a substantial number of the cross-linking molecules combine with acetaldehyde, such that they are disabled as cross-linking agents. This reaction competes with a reaction between the cross-linking agent (e.g., ADH) and cross-linkable species such as DAAM.

To the extent acetaldehyde molecules react with the cross-linking agent, there is simply less of that agent available to participate in such cross-linking reaction, and the extent of cross-linking can be significantly and deleteriously diminished. That diminution can be correlated with a fall-off in the performance of a water-borne composition such as a paint or other coating produced in accordance with the foregoing. Thus, the discovery that the aforementioned problem can be rectified by virtue of effecting cross-linking with a blocked cross-linking agent having at least one hydrazone group incorporated therein is itself a further substantial and innovative advance complementary to the invention described in Parent U.S. application Ser. No. 13/152,856, filed Jun. 3, 2011 (the “Parent Case”).

This is because one of ordinary skill in the art, even had he been in possession of knowledge concerning the blocked cross-linking agent's mitigation of premature cross-linking (per the Parent Case), should have assumed that attempts at effectively cross-linking copolymers made from monomer(s) of which at least one is a vinyl-containing monomer, which yields acetaldehyde as a hydrolysis product, would be futile. However, contrary to such assumption, use of a blocked cross-linking agent enables effective cross-linking even for those polymers, typically copolymers. Due to the realization that disablement of the cross-linking agent's efficacy is caused by the generation of acetaldehyde, along with the realization that the blocked cross-linking agent's hydrazone component is resistant to the action of acetaldehyde, we have been able to cross-link copolymers successfully despite incorporation of the aforementioned vinyl-containing monomer units. It is our belief that a blocked cross-linking agent having a hydrazone group is resistant to reaction with acetaldehyde, and thus is protected against compromise as long as it is maintained in that state. More specifically, the hydrazone group of a blocked cross-linking agent is not reactive (at least to any consequential degree) with the acetaldehyde product formed in hydrolysis of the aforementioned vinyl-containing monomer. Thus, in spite of the presence of acetaldehyde, the cross-linking agent can be protected against depletion prior to the point at which cross-linking is desirably induced—i.e., during or after application of a cross-linkable water-based composition (such as a paint or other coating) to a surface of interest. This is accomplished by maintaining the cross-linking agent in a dormant state, through intentionally impeding the hydrazide form's emergence until such application of the cross-linkable water-based composition.

Serendipitously, the same reaction mechanism which allows for the management of cross-linking's onset, per the Parent Case, also enables one to avoid poisoning of the cross-linking agent for polymers with vinyl-containing monomer units as aforesaid, pursuant to the present invention. Accordingly, our invention can be deployed in conjunction with the invention to which the aforementioned Parent Case is directed.

In certain good embodiments, the conversion of blocked cross-linking agent to uninhibited cross-linking agent is propitiously effected by taking advantage of the reaction dynamics of such conversion. In accordance with this strategy, the equilibrium of the reaction is shifted toward the blocked cross-linking agent prior to application of compositions containing the above-mentioned polymer to a surface and the equilibrium is shifted toward formation of the cross-linking agent in uninhibited form at and after the time when such compositions are applied to a surface.

Though not wishing to be bound or limited by any mechanism or theory, we conclude that because hydrazone does not react with acetaldehyde, the cross-linking agent's potential efficacy is preserved against poisoning. This is by way of the same path via which cross-linking of the polymeric constituents may be inhibited because the hydrazone does not react directly with the carbonyl or epoxy groups on the polymer, with the consequence that cross-linking does not occur to a significant extent, especially within any relevant time-frame. By way of illustration, in a preferred embodiment, the blocked cross-linking agent comprises a hydrazone group and the polymers comprise vinyl alkylester, especially vinyl acetate, groups as well as one or more carbonyl and/or epoxy groups.

Thus, a water-borne composition comprises polymers, especially copolymers, incorporating vinyl-containing monomer units (made from monomers of which at least one is a monomer which yields acetaldehyde as a hydrolysis product) with cross-linking functionality, P₁-R_(CL) and P₂-R_(CL), residual vinyl-containing monomer as aforesaid, and a blocked cross-linking agent, NCLA. Neither the acetaldehyde hydrolysis product, nor the cross-linking functionality, R_(CL), reacts with the blocked cross-linking agent, NCLA. But R_(CL) is capable of reacting with the alternative form cross-linking agent, CLA, to yield the cross-linked polymer P-CL-P, wherein CL is the cross-link between the two polymer chains, P, as follows:

P₁-R_(CL)+P₂-R_(CL)+CLA→P₁-CL-P₂+A  (I)

The cross-linking agent needed for the reaction to proceed is preferably not included, or otherwise present, to any material extent (i.e., to an extent that either more than an inconsequential amount of cross-linking agent would be depleted, or any substantial premature cross-linking would occur) in a water-borne composition according to our invention before its application to a surface. Rather, the cross-linking agent is formed at the desired time under conditions according to the equilibrium reaction between the blocked cross-linking agent and the cross-linking agent in unhibited form:

The equilibrium of the chemical reaction II may be shifted by any change in the prevailing conditions, such as, but not limited to, water concentration, reduction of compound N, reaction of compound CLA, or exposure to visible or ultraviolet light.

It follows that a blocked cross-linking agent is any compound that when present in an aqueous composition comprising a cross-linkable polymer is in a nonreactive (i.e., blocked) state vis-à-vis acetaldehyde and also the polymer, but through an equilibrium reaction can be converted to cross-linking agent in an unhibited form, such that it is capable of reacting with functionality on two or more polymers to link the polymers together.

Cross-Linking and Blocked Cross-Linking Agents

The blocked cross-linking agent can comprise as few as one hydrazone group, and there can optionally be at least one other moiety capable of reacting with the cross-linking functionality of cross-linkable polymer, for instance, a hydrazine moiety. However, in preferred embodiments, the blocked cross-linking agent comprises at least two hydrazone groups. For example, the blocked cross-linking agent may be adipic acid di(propylidene hydrazide). In an aqueous phase or merely with moisture present, adipic acid di(propylidene hydrazide) has the following equilibrium with acetone and adipic acid dihydrazide:

The hydrazone is a blocked cross-linking agent that will not significantly react with either an acetaldehyde hydrolysis product or a polymer comprising functionality such as a carbonyl group or an epoxy group. However, adipic acid di(propylidiene hydrazide), a hydrazone, reacts with the water to form acetone, a ketone, and adipic acid dihydrazide, a hydrazide. The hydrazide, however, is an uninhibited cross-linking agent that is capable of reacting with the carbonyl group or epoxy group of the polymer. The reaction is reversible and the water may be expelled with the hydrazone being reformed. Eventually, the reversible reaction reaches equilibrium between the hydrazone and the hydrazide as shown in Equation III.

Under certain conditions, this reversible reaction has an equilibrium that is strongly shifted leftward or toward the production of the hydrazone and only a small amount (no more than a few, e.g., 5 and preferably 3 percent) hydrazide is present in the water-borne composition. The hydrazone will not react with aforementioned acetaldehyde product, or the carbonyl or epoxy groups of the polymers directly, thus mitigating premature cross-linking of the polymers. In such an embodiment, acetaldehyde reaction with the cross-linking agent, and cross-linking of the polymers, are inhibited. However, during the drying process after application of the composition to a surface, the equilibrium will shift toward the formation of hydrazide groups (NH2NH—) which are capable of reacting with the carbonyl and epoxy groups. This is because during drying, ketone or aldehyde constituents are evaporating and the hydrazide groups are reacting to cross-link the polymers, thus shifting the equilibrium to the formation of additional hydrazide. More hydrazone, and eventually nearly all of the hydrazone, will be converted to hydrazides which react to cross-link the polymers as the film dries and cures.

More specifically, the ketone or aldehyde formed in conversion of the hydrazone to the hydrazide has a low boiling point. With a low boiling point, the ketone or aldehyde evaporates and even though water is also evaporating as the coating dries, reformation of the hydrazone is prevented by depletion of the ketone or aldehyde.

Since depletion of the ketone or aldehyde drives production of the hydrazides it causes completion of the cross-linking reaction. Therefore, the volatility of the ketone or aldehyde will determine the rate and extent of cross-linking. Higher volatility, lower boiling point ketones or aldehydes will result in a high rate of hydrazide formation and an early physical and mechanical property development in the dried products. In certain embodiments, the ketones and aldehydes will have a boiling point below 200° C., a vapor pressure at 25° C. above 1.7 mm Hg, and an evaporation rate (vs. butyl acetate) above 0.1; in further embodiments, the ketones and aldehydes will have a boiling point below 150° C., a vapor pressure at 25° C. above 15 mm Hg, and an evaporation rate (vs. butyl acetate) above 0.2; and in even further embodiments, the ketones and aldehydes will have a boiling point below 100° C., a vapor pressure at 25° C. above 23 mm Hg, and an evaporation rate (vs. butyl acetate) above 0.3.

A suitable blocked cross-linking agent comprising two hydrazone groups has the formula:

and/or the formula:

and a suitable cross-linking agent comprising one hydrazone group and a hydrazine group has the formula:

and/or the formula:

wherein, in any of the embodiments of the cross-linking agents of formulae (IV) to (VII), R is a divalent organic group or a covalent bond and R1, R2, R3, and R4 are independently selected from hydrogen and an organic group. More specifically, R1, R2, R3, and R4 are independently selected from: C1 to C12 linear alkyl, alkenyl, or alkynyl; branched alkyl, alkenyl, or alkynyl having a C1 to C12 primary chain. Alternatively, R1 and R2 or R3 and R4 joined together to form a cyclic organic group. The foregoing species can be unsubstituted, or any hydrogen on the straight or branched alkyl, alkenyl, or alkynyl (including when two are joined together) can be substituted with hydroxyl, amino, phenyl, benzyl, or halogen. For example, R1, R2, R3, and R4 can be independently selected from methyl, ethyl, n-propyl, n-butyl, iso-butyl, tert-butyl, n-amyl, iso-amyl, n-hexyl, n-heptyl, n-octyl, iso-octyl, n-nonyl, n-decyl, n-undecyl or n-dodecyl group and if R1 and R2 or R3 and R4 are a cyclic group, the cyclic group can be cyclopentyl or cyclohexyl. Examples of hydrazones include, but are not limited to, succinic acid di(propylidene hydrazide), oxalic acid di(2-propylidene hydrazide), adipic acid di(2-propylidene hydrazide), adipic acid di(2-butylidene hydrazide), and adipic acid di(4-hydroxy-4-methyl-2-pentylidene hydrazide).

A blocked cross-linking agent can also comprise one hydrazide group and one hydrazone group, for example. The hydrazide group may react with one carbonyl group on the polymer chain but cross-linking does not occur without the reaction of the hydrazone group. That is, cross-linking does not occur until the hydrazone is converted to a second hydrazide group. However, it will be appreciated that such a blocked cross-linking agent's hydrazide group is still subject to reaction with the aforementioned acetaldehyde hydrolysis product. Insofar as that reaction takes place, the opportunity for cross-linking is commensurately lost. Thus, blocked cross-linking agents which have a hydrazide group along the foregoing lines may prove less satisfactory for the present invention, depending on the extent to which the hydrazide group encounters and reacts with acetaldehyde.

The blocked cross-linking agent may be added to the water-borne composition as a liquid, in solid form, or as a slurry such as the blocked cross-linking agent in water.

Hydrazones can be prepared by reacting aldehyde or ketones with di- or multi-hydrazides, such as carboxylic acid di- or multifunctional hydrazides, for instance:

Examples of multifunctional hydrazides include, but are not limited to: C₂-C₁₈ saturated dicarboxylic acid dihydrazides such as oxalic acid dihydrazide, malonic acid dihydrazide, glutaric acid dihydrazide, succinic acid dihyrazide, adipic acid dihydrazide, sebacic acid dihydrazide and the like; monoolefinic unsaturated dicarboxylic acid dihydrazides such as maleic acid dihydrazide, fumaric acid dihydrazide, itaconic acid dihydrazide and the like; terephtalic acid dihydrazide or isophthalic acid dihydrazide; pyromellitic acid dihydrazide, multifunctional hydrazide containing three or more hydrazide groups, trihydrazide or tetrahydrazide, such as citric trihydrazide, nitrilo-acetic trihydrazide, cyclohexanoic tricarboxylic trihydrazide, ethylene diamine tetra-acetic tetrahydrazide and the like; nitrilotrihydrazide, citric acid trihydrazide, 1,2,4-benzene trihydrazide, ethylenediaminetetraacetic acid tetrahydrazide, 1,4,5,8-naphthoic acid tetrahydrazide; polyhydrazides such as those obtained through reaction of low molecular weight polymers having carboxylic acid lower alkyl ester groups with hydrazine or hydrazine hydrate; and polyfunctional semicarbazides.

The hydrazide or dihydrazide can be reacted with a compound of the formula:

wherein R5 and R6 are independently selected to be hydrogen or an organic group, with at least one being an organic group.

Examples of such, organic groups are alkyl groups, preferably of from 1 to 12 carbon atoms, linear or branched, for instance, a methyl, ethyl, n-propyl, n-butyl, iso-butyl, tert-butyl, n-amyl, iso-amyl, n-hexyl, n-heptyl, n-octyl, iso-octyl, n-nonyl, n-decyl, n-undecyl or n-dodecyl group. The alkyl group is more preferably of from 1 to 3 carbon atoms, and most preferably, 1 carbon atom. R5 or R6 can be substituted for instance, by a hydroxy, amino, amine or other functional group. Further, R5 and R6 can be joined together to form a cyclic group such as, but not limited to, cyclopentyl or cyclohexyl.

If either of R5 and R6 is hydrogen, the compound of formula VIII is an aldehyde (an aldehyde is an organic group containing a formyl group, —HCO). Examples of aldehydes include, but are not limited to, acetaldehyde, butyraldehyde, benzaldehyde, cinnamaldehyde, and toluoyldehyde. If both of R5 and R6 are organic, the compound of formula VIII is a ketone. Examples of ketones are acetone, methyl ethyl ketone, diethyl ketone, isopropyl methyl ketone, n-propyl methyl ketone, di-isopropyl and di-n-propyl ketone, tert-butyl methyl ketone, isobutyl methyl ketone, sec-butyl methyl ketone and diisobutyl ketone, diacetone alcohol, cyclohexanone, 1-propanone, 2-propanone and acetophenone.

In various embodiments a method of forming a water-borne composition comprises adding a hydrazone to the composition. The hydrazone can be added in any form, however, there may be advantages to adding the hydrazone in a solid form. The hydrazone may be added as a solid such as in a powder form or as a slurry such as an aqueous slurry or dispersion of hydrazone. The hydrazone may also be formed in situ in the water-borne composition. However, as mentioned above, adding the hydrazone in solid form has several advantages, for example, avoiding the use of flammable materials, such as acetone, at the point of formulation of the water-borne composition, allowing more precise control of the hydrazone formation and over stoichiometric conversion of the hydrazide to hydrazone, as well as better control over side reactions and by-product formation, and reducing premature cross-linking in the water-borne composition.

Cross-Linkable Polymers

The invention to which the Parent Case is directed contemplates use with a wide range of cross-linkable polymers, to with, any polymer comprising functionality that is capable of reacting with the reactive cross-linking agent and does not significantly react with the blocked cross-linking agent. Suitable polymers that will react with the hydrazide cross-linking agent include polymers that contain carbonyl groups such as ketone or aldehyde groups and/or epoxy groups. The cross-linking interaction can be between polymer moieties (e.g., portions or segments) of a single polymer unit (for instance, a chain), or moieties of or constituting different polymer units, such as a first polymer chain and a second polymer chain. On the other hand, while the present invention can be practiced compatibly with all such copolymers, it is especially suited to the invigoration of cross-linking of copolymers formed (at least in part) from vinyl-containing monomers which yield acetaldehyde as a hydrolysis product.

The following passages are devoted to the identification of exemplified monomer units and copolymers made therefrom which are suitable for the invention to which the Parent Case is directed. That identification is made more specific through confirmation of exemplified monomer units and copolymers as to which our present invention is especially efficacious.

Examples of the aforementioned wide range of polymers comprising at least one carbonyl and/or epoxy group are vinyl, acrylic, and/or styrenenated copolymers containing monomer units of a vinyl alkyl ketone in which the alkyl is of from one to twenty (preferably, one to eighteen) carbons, including, but not limited to, vinyl methyl ketone, vinyl ethyl ketone and/or vinyl butyl ketone; vinylaceto acetate, acetoacetoxyethyl acrylate, acetoacetoxyethyl methacrylate, and mixed esters of aliphatic diols with (meth)acrylic acid and acetoacetic acid; (meth)acrolein, crotonaldehyde, diacetone acrylamide, diacetone(meth)acrylamide, diacetone(meth)acrylate, anhydride monomers such as maleic or halomaleic anhydride monomers, or any other vinyl or acrylic monomer unit containing at least one carbonyl. Out of the foregoing, examples for which our invention is especially efficacious are copolymers formed from monomers of which at least one is a vinyl-containing monomer such as the above-mentioned vinyl alkyl ketones.

Polymers having epoxy groups are also within the aforementioned wide range of suitable materials. These can be made from epoxy-containing polymerizable unsaturated monomers, which include, but are not limited to, compounds having one epoxy group and one polymerizable unsaturated group per molecule. For example, glycidyl meth(acrylate), β.-methylglycidyl meth(acrylate), 3,4-epoxycyclohexylmethyl meth(acrylate), 3,4-epoxycyclohexylethyl meth(acrylate), 3,4-epoxycyclohexylpropyl meth(acrylate), allylglycidyl ether, and the like, can be used either singly or in combination of two or more.

Also, ethylenically unsaturated monomers such as (meth)acrylates, styrenenated monomers, and vinyl esters can be used as co-monomers. Examples of (meth)acrylates include various (C₁-C₂₀)alkyl or (C₃-C₂₀)alkenyl esters of (meth)acrylic acid; for example, methyl(meth)acrylate, ethyl(meth)acrylate, n-propyl(meth)acrylate, isopropyl(meth)acrylate, n-butyl(meth)acrylate, isobutyl(meth)acrylate, pentyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, decyl(meth)acrylate, dodecyl(meth)acrylate, stearyl(meth)acrylate, α-chloroethyl(meth)acrylate, cyclohexyl(meth)acrylate, phenyl(meth)acrylate, methoxyethyl(meth)acrylate, ethoxyethyl(meth)acrylate, methoxypropyl(meth)acrylate, ethoxypropyl(meth)acrylate lauryl acrylate, methyl methacrylate, butyl methacrylate, ethyl methacrylate, isodecyl methacrylate, and lauryl methacrylate. The expression (meth)acrylic acid is intended to serve as a generic expression embracing both acrylic and methacrylic acid. Similarly, the expression (meth)acrylate is intended as a generic expression embracing both acrylic acid and methacrylic acid esters. Examples of styrenated monomers include styrene, alkylstyrenes (e.g., α-ethylstyrene, α-methylstyrene, vinyl toluene, 2,4-dimethylstyrene, 4-t-butylstyrene, and the like), and halostyrenes (e.g., α-bromostyrene, 2,6-dichlorostyrene, and the like). Examples of vinyl esters include vinyl carboxylate alkyl ethers (e.g., vinyl acetate, vinyl propionate, vinyl butyrates, vinyl benzoates, halo-substituted versions thereof such as vinyl chloroacetate, and the like), and Veova monomers. Other ethylenically unsaturated monomers that can be used as co-monomers include carboxylic group-containing of monomers, hydroxyl group-containing monomers, amide group-containing monomers, and amino group-containing monomers. The vinyl esters mentioned above in this paragraph, preferably vinyl alkyl esters or vinyl carboxylate ethers, such as those in which the alkyl is of from one to eighteen carbons, especially vinyl acetate, are examples for which the present invention is especially efficacious.

Other polymers comprising carbonyl and/or epoxy groups can also be used for this invention. Examples are polyurethane or polyurethane dispersions, acrylic/urethane hybrids, alkyd/urethane hybrids, alkyds, polyesters, and water dispersible epoxy.

Primer latexes are water-borne compositions used for coating surfaces. Primer latexes typically comprise lower molecular weight, soft polymers. The lower molecular weight polymers are more readily absorbed into a substrate, thereby providing strong adhesive and chalk binding properties. Therefore, embodiments of the primer latexes comprise water, low molecular weight polymer comprising cross-linking functionality, and a blocked cross-linking agent comprising at least one first functional group that is not capable of reacting with the reactive functional group on the polymer and is capable of converting to a second functional group, wherein the second functional group is capable of reacting with the reactive functional group through an equilibrium reaction.

The molecular weight of the polymers in the primer latex should be low enough to allow at least partial absorption of the polymers into the substrate yet still high enough to provide a coherent coating. In certain embodiments, the low molecular weight polymer has a number average molecular weight of less than 100,000 Daltons. In further embodiments, the low molecular weight polymer has a number average molecular weight of less than 50,000 Daltons. In still further embodiments, the low molecular weight polymer has a number average molecular weight of less than 25,000 Daltons.

The low molecular weight polymers in the primer latex may further comprise a low glass transition temperature, Tg. The glass transition temperature is the temperature at which the amorphous domains of the polymer take on the characteristic properties of the glassy state—brittleness, stiffness, and rigidity. Low molecular weight polymers with a low glass transition temperature provide the primer latex with strong adhesion, chalk binding, flexibility and toughness. In certain embodiments, the latex primer comprises polymers with a glass transition temperature less than 10° C. In further embodiments, the latex primer comprises polymers with a glass transition temperature less than 6° C. In still further embodiments, the latex primer comprises polymers with a glass transition temperature less than 4° C. The glass transition temperature is determined on a Differential Scanning calorimeter. An example of a latex primer was produce as described in Example 14, wherein the primer latex comprises a polymer having a number average molecular weight 24,700 g/mol, a weight average molecular weight 60,400 g/mole, and a Tg of 1.7° C.

The primer latex may comprise a hydrazone cross-linking agent as described above and polymers comprising polymers that will react with the hydrazide cross-linking agent include polymers that contain carbonyl groups such as having ketone or aldehyde groups and/or epoxy groups.

EXAMPLES Example 1 Preparation of dihydrazone, succinic acid di(2-propylidene hydrazide)

Succinic acid di(2-propylidene hydrazide) was prepared by the reaction of 2-propanone with succinic acid dihydrazide. The general process for production of the dihydrazone in these examples is to mix a dihydrazide with water and subsequently add the ketone or aldehyde. 60 grams of water and 40 grams of succinic acid dihydrazide were added to a stainless steel flask. An agitator in the stainless steel flask mixed the ingredients for 10 minutes. Under continued mixing, 16 grams of 1-propanone was added to the flask. A white dispersion was formed. The dispersion was filtered to collect a white powder. The powder was then dried at 40° C. under vacuum for 24 hours. The final product was a white powder of succinic acid di(2-propylidene hydrazide) which has the chemical structure:

Example 2 Preparation of dihydrazone, oxalic acid di(2-propylidene hydrazide)

The process was the same as in Example 1, except 40 grams of water, 20 grams of oxalyl dihydrazide, and 10 grams of 2-propanone were used. The final product was a white powder of oxalic acid di(2-propylidene hydrazide) with the chemical structure:

Example 3 Preparation of dihydrazone, adipic acid di(2-propylidene hydrazide)

The process was the same as in Example 1, except 100 grams of water, 40 grams of adipic acid dihydrazide, and 36 grams of 2-propanone were used. The final product was a white powder of adipic acid di(2-propylidene hydrazide).

Example 4 Preparation of Blocked Cross-Linking Agent Comprising One Hydrazone and One Hydrazine Group

The process was the same as in Example 1, except 100 grams of water, 40 grams of adipic acid dihydrazide, and 13.5 grams of 2-propanone were used. The mole ratio of adipic acid dihydrazide to 2-propanone was 2 to 1. The primary product has a chemical structure:

Example 5 Preparation of a Mixture of a Blocked Cross-Linking Agent Comprising a Dihydrazone and a Blocked Cross-Linking Agent Comprising One Hydrazone and One Hydrazine Group

The process is the same as in Example 1, except 62.7 grams of water, 25 grams of adipic acid dihydrazide, and 12.3 grams of 2-propanone were used. The mole ratio of adipic acid dihydrazide to 2-propanone was 1.5 to 1. The final product was a mixture of the products in Example 3 and Example 4.

Example 6 Preparation of adipic acid di(2-propylidene hydrazide) dispersion

In a stainless steel flask equipped with an agitator, 58.6 grams of water were added, the agitator was turned on, then 25 grams of adipic acid dihydrazide were added. The mixture was agitated for at least 10 minutes until a stable dispersion was formed. 16.4 grams of 2-propanone were then added under mixing. A clear solution formed after a few minutes. Mixing was continued for at least another hour until reaction product precipitated and formed a stable dispersion.

Example 7 Preparation of adipic acid di(2-butylidene hydrazide) dispersion

The procedure is the same as in Example 6, except 28 grams of water, 3 grams of methyl ethyl ketone, and 1.5 grams of adipic acid dihydrazide were used. The final reaction product was an aqueous dispersion of adipic acid di(2-butylidene hydrazide) having the following chemical structure:

Example 8 Preparation of adipic acid di(4-Hydroxy-4-methyl-2-pentylidene hydrazide) dispersion

The procedure was the same as in Example 6, except 28 grams of water, 2.4 grams of 4-Hydroxy-4-methyl-2-pentane (diacetone alcohol), and 1.5 grams of adipic acid dihydrazide were used. The final reaction product was an aqueous dispersion of adipic acid di(4-Hydroxy-4-methyl-2-pentylidene hydrazide) with the chemical structure:

Example 9 Preparation of Paints with Polymer Comprising a Ketone Group and with a Conventional Cross-Linking Agent Adipic Acid Dihydrazide Comparative Example

A water-borne paint comprising an acrylic copolymer (49% solids by weight) latex made from 49% methacrylate (MMA), 48% 2-ethyl hexylacrylate (2EHA) and 3% diacetone acrylamide (DAAM) was prepared. A conventional cross-linking agent, adipic acid dihydrazide, was used in the paint. The batch size is 100 gallons.

TABLE 1 Paint formula for Example 9 Ingredient lbs WATER 70 KATHON LX 1.5% (biocide) 1 Potassium Triphosphate 1 TAMOL 1124 (dispersant) 12 IGEPAL CO-630 (surfactant) 3.5 TI-PURE R-706 (Titanium dioxide) 285 ATTAGEL 50 (extender pigment) 5 FOAMSTAR A-45 (deformer) 1.5 BYK-420 (rheology additive) 2.6 Grind for 15 minute, then add following ingredient in a thin- down container PROPYLENE GLYCOL 2.5 WATER 55 EASTMAN EEH SOLVENT (coalescence) 6 Acrylic latex (49% solids) 440 EASTMAN OPTIFILM 400 (Plasticizer) 8 AMMONIA HYDROXIDE (29%) 1 ADIPIC ACID DIHYDRAZIDE 6 ACRYSOL RM-5000 (rheology additive) 19 ACRYSOL RM-825 (rheology additive) 3 FOAMSTAR A-45 2 BYK-022 (deformer) 6 WATER 180 POLYPHASE 663 (midewcide) 4.75

Example 10 Preparation of Paints with Polymer Comprising a Ketone Group and with a Dihydrazone Blocked Cross-Linking Agent

A water-borne paint was made, comprising the same acrylic copolymer and paint formula as in Example 9 except that adipic acid dihydrazide was replaced by 24 lbs of adipic acid di(2-propylidene hydrazide) dispersion from Example 6, and the amount of water in the thin-down was reduced by 18 lbs to adjust the volume of paint to 100 gallon.

Example 11 Scrubability of Paints of Example 9 and Example 10

The scrub tests were performed for the paints of Example 9, prior art paint comprising a dihydrazide cross-linking agent, and Example 10, water-borne paint comprising a dihydrazone blocked cross-linking agent. The tests were done on fresh prepared paints, and paint aged for six months. The scrub test was performed using ASTM D2486 Method B on 7-mil paint draw downs dried for 7 days. A BYK-Gardner Abrasion Tester with a boat weighing 1000 grams was used for the test. The scrub cycle number at failure was recorded (where the paint film was removed and the surface of the underlying substrate shows through). A higher cycle number indicates a better scrub resistance for the paint.

TABLE 2 Scrub Cycles of Paints Example 9 Time paint (comparative aged Example 10 example) Fresh paint 1410 1427 1 week 1319 854 1 month 1400 867 2 month 1178 800 3 month 1488 615 5 month 1353 302 6 month 1543 491

As shown in Table 2, the scrubability of the paint prepared in Example 10 remained unchanged for paint aged up to 6 months. The scrubability of the comparative example, Example 9, started to drop after being aged for one week, and continued to decrease afterwards.

Example 12 Preparation of Paints Using Various Hydrazones

The polymer used in paints of Example 12 was an acrylic latex polymer containing MMA 48.1%, 2-EHA 47.9%, DAAM 4% by weights. The latex polymer had solids of 49% w/w. The batch size was 50 gallons. The formulas for each of the paints are listed in Table 3.

Summary of Example Paints.

Example 12A, the blocked cross-linking agent was adipic acid di(2-propylidene hydrazide) dry powder prepared in Example 3 in powdered form.

In Example 12B, the blocked cross-linking agent was adipic acid di(2-butylidene hydrazide) in an aqueous dispersion prepared in Example 7. Total amount of water was reduced to adjust the volume to 50 gallons.

In Example 12C, the blocked cross-linking agent was adipic acid di(2-propylidene hydrazide) in an aqueous dispersion prepared in Example 6.

In Example 12D, the blocked cross-linking agent was of adipic acid di(4-hydroxy-4-methyl-2-pentylidene hydrazide) in an aqueous dispersion prepared in Example 8. Total amount of water was reduced to adjust the volume to 50 gallons.

In Example 12E, the multi-functional hydrazones may be prepared during paint formulation. The reactants of adipic acid dihydrazide and 2-propanone were added during formulation of the paint product. The reaction product, adipic acid di(2-propylidene hydrazide) was formed in the paint making process.

Example 12F is a comparative example using a conventional cross-linking agent adipic acid dihydrazide.

TABLE 3 Paints of Example 12 Ingredient A B C D E F WATER 29.7 lbs 29.7 lbs 29.7 lbs 29.7 lbs 29.7 lbs 29.7 lbs KATHON LX 1.5% (biocide) 0.6 0.6 0.6 0.6 0.6 0.6 TAMOL 165A (dispersant) 6.0 6.0 6.0 6.0 6.0 6.0 FOAMSTAR A-45 (defoamer) 0.6 0.6 0.6 0.6 0.6 0.6 TRONOX CR-826 (TiO2) 134.2 134.2 134.2 134.2 134.2 134.2 ASP 170 (extender pigment) 13.5 13.5 13.5 13.5 13.5 13.5 POTASSIUM CARBONATE 0.8 0.8 0.8 0.8 0.8 0.8 Grind for 20 min, then add 220.1 220.1 220.1 220.1 220.1 220.1 Acrylic Polymer (MMA/EHA/DAAM) OPTIFILM ENHANCER 400 (plasticizer) 5.0 5.0 5.0 5.0 5.0 5.0 Example 3 1.9 — — — — — Example 7 — 32.5 — — — — Example 6 4.8 — — — Example 8 — — — 31.9 — — 2-PROPANONE — — — — 1.2 — ADIPIC ACID DIHYDRAZIDE — — — — 1.5 1.5 BYK-022 (defoamer) 3.0 3.0 3.0 3.0 3.0 3.0 WATER 33.4 33.4 33.4 33.4 33.4 33.4 ACRYSOL RM-2020 NPR (rheology 7.5 7.5 7.5 7.5 7.5 7.5 additive) ACRYSOL RM-8W (rheology additive) 12.5 12.5 12.5 12.5 12.5 12.5 POLYPHASE 678 (mildewcide) 1.0 1.0 1.0 1.0 1.0 1.0 WATER 66.9 36.1 64.9 36.1 66.1 67.6

The scrubability was tested for aged paints in Example 12. The test method and conditions were the same as in Example 11. As can be seen in Table 4, the paint films produced by the water-borne paints of Example 12A, B, C, and E, using various hydrazones, have significantly higher scrubs than the paint film produced by the paint film of Example 12F which used a conventional cross-linking agent, adipic acid dihydrazide.

Example 12D had relatively lower scrub cycles. Adipic acid di(4-hydroxy-4-methyl-2-pentylidene hydrazide) yielded a by-product of 4-hydroxy-4-methyl-2-pentanone in water. 4-Hydroxy-4-methyl-2-pentanone has a relatively high boiling point at 166° C., and lower evaporation rate of 0.12 (vs. n-butyl acetate). In preferred embodiments, the by-product ketone should evaporate in order to shift the equilibrium in Equation III to the right side. The low volatility of 4-hydroxy-4-methyl-2-pentanone may have reduced the rate of cross-linking in the film.

TABLE 4 Scrubability of Aged Paints in Example 12 Scrub cycle Aged for Aged for Example Cross-linking agent 2 months 4 months A adipic acid di(2-propylidene 1150 Not tested hydrazide) dry powder B adipic acid di(2-butylidene hydrazide) 1300 1219 dispersion C adipic acid di(2-propylidene 1322 1061 hydrazide) dispersion D adipic acid di(4-Hydroxy-4-methyl-2- 393 Not tested pentylidene hydrazide) dispersion E adipic acid di(2-propylidene 1074 Not tested hydrazide) Prepared in Paint F Adipic acid dihydrazide 804  539 (comparative)

Example 13 Latex Polymer with Ketone Groups on the Polymer Chains and Dihydrazone in Aqueous Phase

A styrene acrylic polymer containing DAAM was prepared according to the recipe in Table 5 by emulsion polymerization.

The emulsion polymerization was carried out in a four-neck flask under nitrogen purge. The reaction flask was equipped with a condenser, a thermometer, an agitator and a feeding pump. The flask was immersed in a temperature controlled water bath maintained at a constant temperature within about ±0.1° C. of the set point.

The reaction started with charging deionized water, ADEKA SR-10, and sodium bicarbonate to the reaction flask. The reactor was heated to 75° C. under agitation. 5% w/w of the monomer mix was charged to the reactor. After mixing for 5 minutes, the Initiator Solution 1 shown in Table 5 was added to the reaction flask to start the polymerization.

Fifteen minutes after the start of the reaction, the remaining monomer mix and Initiator Solution 2 shown in Table 5 were fed to the reaction flask over a period of 3.5 hours. The temperature of the reaction flask was then maintained at 80-85° C. for one hour after which it was cooled to about 65° C. Chaser solutions made from oxidizing agent and reducing agent were fed to the reaction flask over 30 minutes. The reaction contents were then cooled to 35° C. and sodium hydroxide/water solution was added.

Adipic acid dihydrazide solution was then added as the cross-linking agent.

TABLE 5 Component Parts (by weight) Initial Charge in Reactor Deionized water 32.8 ADEKA SR-10 (surfactant) 0.02 Sodium bicarbonate 0.02 Monomer Mix Deionized water 10.5 Diacetone acrylamide 1.7 ADEKA SR-10 0.6 Ethylmethacrylate phosphate 30% 0.2 (Sipomer PAM-4000) ADEKA ER-30 (surfactant) 0.6 Methacrylic acid 0.2 Methylmethacrylate 12.4 Butyl acrylate 21.4 Styrene 10.2 Wet adhesion monomer 50%, (Rohm & Haas 1.1 (now Dow Chemical Company), QM-1458) Initiator Solution 1 Ammonium persulfate 0.1 Deionized water 0.4 Initiator Solution 2 Ammonium persulfate 0.1 Deionized water 0.8 Chaser solutions 1) Oxidizing agent t-butylperoxide 0.06 Deionized water 0.4 2) Reducing agent Bruggolite ® FF6M 0.04 Deionized water 0.6 Pre-mix Sodium hydroxide solution 50% 0.2 Deionized water 2.0 Adipic acid di(2-propylidene hydrazide) 2.4 Total 100

The final product is a cross-linkable latex paint.

Example 14 Low MW Latex Polymer with Ketone Group Using Diacetone Acrylamide

An acrylic polymer containing DAAM was prepared according to the recipe in Table 6 by emulsion polymerization. The emulsion polymerization was carried out in a four-neck flask under nitrogen purge. The reaction flask was equipped with a condenser, a thermometer, an agitator and a feeding pump. The flask was immersed in a temperature controlled water bath maintained at a constant temperature within about ±0.1° C. of the set point.

The reaction starts with charging deionized water, Rhodacal® DS4 to the reaction flask. The contents of the reactor were heated to 75° C. under agitation. 5% w/w of the monomer mix was charged. After mixing for 5 minutes, the Initiator Solution 1 shown in Table 6 was added to the reaction flask to start the seed polymerization.

15 minutes after the start of the reaction, the remaining monomer mix, and Initiator Solution 2 shown in Table 6, were fed to the reaction flask over a period of 3.5 hours. A small amount of water was used to rinse the monomer mix flask. The temperature of the reaction flask was then maintained at 80-85° C. for one hour after which it was cooled to about 65° C. Chaser solutions made from oxidizing agent and reducing agent were fed to the reaction flask over 30 minutes. The reaction contents were then cooled to 35° C. and ammonia solution was added.

The polymer has the number average molecular weight 24,700 g/mol, a weight average molecular weight 60,400 g/mol, and a Tg of 1.7° C. as determined on a Differential Scanning calorimeter.

TABLE 6 Emulsion polymerization of an acrylate polymer with Diacetone acrylamide Component Parts (by weight) Initial Charge in Reactor Deionized water 760 Rhodacal ® DS4 (23% w/w) 1.2 Monomer Mix Deionized water 200 Diacetone acrylamide 30 Rhodacal ® DS4 (23% w/w) 40 Rhodafac RS-610-25A (phosphate surfactant) 20 Rhodasurf BC-729 (surfactant from Rhodia) 3 Methacrylic acid 12 Methyl methacrylate 500 2-Ethyl hexylacrylate 570 Wet adhesion monomer 50% w/w, 25 (Visiomer MEEU 50W, Evonik) Isooctyl 3-mercapto propionate 8 Initiator Solution 1 Ammonium persulfate 2.5 Deionized water 30 Initiator Solution 2 Ammonium persulfate 2.5 Deionized water 30 Chaser solutions 1) Oxidizing agent t-butylperoxide 1.4 Deionized water 10 2) Reducing agent Bruggolite ® FF6M 1.0 Deionized water 15 Ammonia hydroxide solution 29% 10 Deionized water (rinse) 10

Example 15 Low MW Latex Polymer with Ketone Group Using Acetoacetoxyethyl Methacrylate

In Example 15, acetoacetoxyethyl methacrylate was used in an acrylic polymer formula as shown in Table 7.

The process of making the latex polymer is the same as in Example 14.

TABLE 7 Emulsion polymerization of acrylic latex polymer with acetoacetoxytethyl methacrylate Component Parts (by weight) Initial Charge in Reactor Deionized water 900 TRITON ™ QS-44 (surfactant from Dow Chemical) 1 Sodium Bicarbonate 4 Monomer Mix Deionized water 330 TRITON ™ QS-44 14 Igepal CO-630 (surfactant from Rhodia Inc.) 8.5 Ammonia hydroxide 29% 30 Acetoacetoxytethyl methacrylate 111 Methacrylic acid 14 Methyl methacrylate 500 Butyl Acrylate 660 Wet adhesion monomer 50% w/w, 26 (WAM (IV) from Air Product) Isooctyl 3-mercapto propionate 11 Initiator Solution 1 Sodium persulfate 3.5 Deionized water 30 Initiator Solution 2 Sodium persulfate 3.5 Deionized water 30 Chaser solutions 1) Oxidizing agent t-butylperoxide 6.5 Deionized water 30 2) Reducing agent Sodium formaldehyde sulfoxylate 4.5 Deionized water 20

Example 16 Low MW Latex Polymer with Ketone Group and Epoxy Group Using Acetoacetoxyethyl Methacrylate and Glycidyl Methacrylate

In Example 16, acetoacetoxyethyl methacrylate and glycidyl methacrylate were used in an acrylic polymer formula as shown in Table 8.

The process of making the latex polymer is the same as in Example 14.

TABLE 8 Emulsion polymerization of acrylic latex polymer with acetoacetoxytethyl methacrylate and glycidyl methacrylate Component Parts (by weight) Initial Charge in Reactor Deionized water 900 TRITON ™ QS-44 (surfactant from Dow Chemical) 1 Sodium Bicarbonate 4 Monomer Mix Deionized water 330 TRITON ™ QS-44 15.3 Igepal CO-630 (surfactant from Rhodia Inc.) 8.5 Ammonia hydroxide 29% 30 Acetoacetoxytethyl methacrylate 40 Glycidylmethacrylate 13.5 Methacrylic acid 20 Methyl methacrylate 500 Butyl Acrylate 660 Wet adhesion monomer 50% w/w, 26 (WAM (IV) from Air Product) Isooctyl 3-mercapto propionate 12 Initiator Solution 1 Sodium persulfate 3.5 Deionized water 30 Initiator Solution 2 Sodium persulfate 3.5 Deionized water 30 Chaser solutions 1) Oxidizing agent t-butylperoxide 6.5 Deionized water 30 2) Reducing agent Sodium formaldehyde sulfoxylate 4.5 Deionized water 20

Example 17 Paint Composition Containing Hydrazone Blocked Crosslinker and Polymer with Ketone Group

Example 17 describes a paint composition containing an acrylic polymer of the Example 14 and a cross-linker of Example 3. In the paint composition's formulation, the order of addition of the various components, is described in Table 9.

Example 18 Paint Composition Containing Hydrazine Crosslinker And Polymer with Ketone Group Comparative Example

Example 18 is a comparative paint composition containing an acrylic polymer of the Example 14 and a conventional cross-linker having a hydrazine group (—NHNH2), adipic acid dihydrazide. In the paint composition's formulation, the order of addition of the various components is described in Table 9.

Example 19 Paint Composition Containing a Commercial Polymer for Primers Comparative Example

Example 19 is a comparative paint composition containing a commercial polymer designed to be a primer, tested for chalk adhesion. In the paint composition's formulation, the order of addition of the various components is described in Table 9.

TABLE 9 Example Example Example Description 17 18 19 WATER 234 lbs 234 lbs 234 lbs NATROSOL PLUS 330 (thickener) 3.5 3.5 3.5 SODIUM BENZOATE 2.0 2.0 2.0 NUOSEPT 95 1.0 1.0 1.0 MIX 5-10 MINUTES ON HIGH 0.0 0.0 0.0 SPEED TAMOL 681 6.0 6.0 6.0 ZN OXIDE SOGEM EPM-E 9.0 9.0 9.0 TRONOX CR-826 122.0 122.0 122.0 OPTIWHITE P 90.0 90.0 90.0 FOAMASTER V (Cognis) 1.0 1.0 1.0 Grind for 20 minute 1.1 1.1 1.1 Thin-Down TRITON CF-10 Commercial Tanning Blocking — — 408 Polymer 43% w/w Polymer of Example 14, 49% w/w 345 345 ROPAQUE OP-96 49.0 49.0 49.0 TEXANOL Eastman Chemical 7.9 7.9 7.9 WATER 64.4 117.4 64.4 ADIPIC ACID DIHYDRAZIDE 3.0 Cross-linker of Example 3 12 NATROSOL PLUS 330 1 0 2.0 WATER 50 6.8 6.8 DREWPLUS L 475 FOAM 3.3 3.3 3.3 Total weight lbs 1002 1002 1011 Total Volume gallon 100 100 100

Example 20 Adhesion Test

Chalk binding tests are typically performed on chalky substrates. Chalky substrates are commercial alkyd paints that have been naturally weathered to achieve an ASTM chalk rating of about from 1-10, with 1 being the worst chalk board. A suitable test method is described in U.S. Pat. No. 6,268,420, the test method is hereby incorporated by reference.

In these cases, chalky substrates are western red cedar panels painted with commercially available alkyd paints and weathered to have ASTM ratings using the method described in the '420 patent. Various 3-mil thick draw down coatings of paint compositions were applied to these panels and let dry for about 7 days at ambient conditions. After drying, adhesion of the paint was evaluated using Scotch™ 600 tape and a 6×6 cross-hatch adhesion standard test, as detailed in ASTM D3359 Method B. For wet chalk adhesion, the coated panels were placed in a fog box, simulating rain conditions at 100% humidity, for about 4 hours and were dried in air at ambient conditions for about 1 hour prior to the crosshatch adhesion test. The percentage peeling (area) for coatings made from each of the paint compositions of Examples 16, 17 and 18 are listed in Table 10 (0% is best, 100% is very poor).

TABLE 10 Chalk adhesion Example 16 Example 17 Example 18 Dry Chalk Adhesion (#2 chalk board) Fresh paint 0% 0% 100%  1 month aged paint 0% 0% — Wet Chalk Adhesion (#2.8 chalk board) Fresh paint 0% 0% 50% 1 month aged paint 0% 40% 80%

Example 21 Preparation of Adipic Acid di(2-propylidene hydrazide) Dispersion with a Rheology Additive

In a stainless steel flask equipped with an agitator, 54.6 grams of water were added, the agitator was turned on, then 25 grams of adipic acid dihydrazide were added. The mixture was agitated for at least 10 minutes until a stable dispersion was formed. 16.4 grams of 2-propanone were then added under mixing. A clear solution formed after a few minutes. Mixing was continued for at least another hour until reaction product precipitated and formed a stable dispersion. 4 grams of AQUAFLOW NLS-200 (rheology additive) were added to the dispersion under agitation.

The slurry dispersion has improved anti-settling property behavior.

Example 22 Preparation of Adipic Acid di(2-propylidene hydrazide) Dispersion with a Latex and a Rheology Additive

In a stainless steel flask equipped with an agitator, 45.6 grams of water were added, the agitator was turned on, then 25 grams of adipic acid dihydrazide were added. The mixture was agitated for at least 10 minutes until a stable dispersion was formed. 16.4 grams of 2-propanone were then added under mixing. A clear solution formed after a few minutes. Mixing was continued for at least another hour until reaction product precipitated and formed a stable dispersion. The temperature of the dispersion was allowed to drop to 105° F. or below, and 10 grams of an acrylic latex containing 51% of methacrylate and butyl acrylic polymer were added, followed by 3.0 grams of AQUAFLOW NLS-200. The Stormer viscosity of the dispersion was 105 Kreb units at 77° F.

The slurry dispersion has improved anti-settling property behavior.

EXAMPLES Example 23 Vinyl Acrylic Copolymer with Ketone or Carbonyl Functional Groups from DAAM

A copolymer was prepared from vinyl acetate, butyl acrylate and 3.5% diacetone acrylamide by weight, in accordance with following Table 11 by emulsion polymerization.

The emulsion polymerization was carried out in a four-neck flask under nitrogen purge. The reaction flask was equipped with a condenser, a thermometer, an agitator, two dropping funnels, and a feeding pump. The flask was immersed in a temperature controlled water bath maintained at a constant temperature within about ±0.1° C. of the set point.

Deionized water and a cellulose colloidal stabilizer were charged to the flask, and the temperature was raised to 75° C. under mixing. After the cellulose dissolved completely and formed a clear solution, phosphate ester surfactant, non-ionic surfactant, and sodium bicarbonate were charged to the reaction flask. 5% by weight of the Monomer Mixture was charged to the reaction flask. After mixing for 5 minutes, Initiator Solution 1 was added to the reaction flask to start the polymerization.

15 minutes after the start of the polymerization reaction, the remaining Monomer Mixture and Initiator Solution 2 were fed to the reaction flask through a monomer pump and a dropping funnel separately over a period of 3.5 hours. Beginning at 30 minutes after the initiation of Monomer Mixture feed, the Wet Adhesion Monomer solution was fed to the through a dropping funnel over 3 hours. The temperature of the reaction flask was maintained at 75° C. during 3.5 hours of Monomer Mixture fee and for an additional hour after the feed was complete. The reaction flask was then cooled to 60° C. Chaser-Oxidizing Agent and Chaser-Reducing Agent solutions were fed to the reaction flask over a 30 minute period simultaneously. The flask was then cooled to room temperature.

The latex copolymer had 52.5% solids content, comprising 3.5% DAAM by weight.

TABLE 11 Vinyl acrylic copolymer with 3.5% DAAM Component Parts (by weight) Initial Charge in Reactor Deionized water 34.0 Cellulose colloidal stabilizer 0.3 Phosphate ester surfactant (25% w/w) 0.1 Non-ionic surfactant 1 0.1 Sodium bicarbonate 0.1 Monomer Mixture Deionized water 5.9 Non-ionic surfactant 1 0.3 Phosphate ester surfactant (25% w/w) 0.2 Non-ionic surfactant 2 0.1 Ionic/non-ionic surfactant blend 1.4 Vinyl acetate 42.9 Butyl acrylate 5.6 Diacetone acrylamide 1.8 Wet Adhesion Monomer Solution Deionized water 1.9 Wet adhesion monomer (50% w/w) 0.8 Initiator Solution 1 Deionized water 1.4 Sodium persulfate 0.05 Initiator Solution 2 Deionized water 2.2 Sodium persulfate 0.05 Chaser-Oxidizing Agent t-butylperoxide 0.0 Deionized water 0.4 Chaser-Reducing Agent Bruggolite ® FF6M 0.0 Deionized water 0.4 Total 100.0

Example 24 Vinyl Acrylic Copolymer with Ketone or Carbonyl Functional Groups from AAEM

The copolymer was prepared from the same constituents and by the same method steps as in Example 23, except 2.6 grams of AAEM was substituted for the DAAM of Example 23.

The product latex copolymer contained 5% AAEM by weight on solids.

Example 25 Vinyl Acrylic Copolymer with 5% DAAM by Weight

The copolymer was prepared from the same constituents and by the same method steps as in Example 23, except 2.6 grams of DAAM, which constitutes 5% by weight of the polymer solids, were incorporated. The latex polymer had 52.5% solids.

Example 26 Vinyl Acrylic Copolymer with Ketone or Carbonyl Functional Groups from DAAM and ADPH

The polymer was prepared from the same constituents, and by the same method steps, as in Example 25. After the reaction flask was cooled to room temperature, 4 grams of a 41% w/w aqueous dispersion of ADPH was added to the latex polymer.

Example 27 Vinyl Acrylic Copolymer with 2.5% DAAM by Weight

The polymer was prepared in the same composition and with the same method as in Example 23, except 1.4 grams of DAAM was used. The latex polymer has 52.5% solids and contained 2.5% DAAM by weight.

Example 28 Comparative Vinyl Acrylic Copolymer

A vinyl acetate and butyl acrylate copolymer, free of cross-linkable ketone or carbonyl functional groups from DAAM or AAEM, was prepared by the same method steps as in Example 23. The constituents from which the copolymer was formulated are identified in Table 12.

TABLE 12 Comparative vinyl acetate and butyl acrylate copolymer Component Parts (by weight) Initial Charge in Reactor Deionized water 34 Cellulose colloidal stabilizer 0.3 Phosphate ester surfactant (25% w/w) 0.1 Non-ionic surfactant 0.1 Sodium bicarbonate 0.1 Monomer Mixture Deionized water 9.1 Non-ionic surfactant 0.2 Phosphate ester surfactant (25% w/w) 0.1 Ionic/non-ionic surfactant blend 0.5 Vinyl acetate 42.7 Butyl acrylate 5.6 Wet Adhesion Monomer Solution Deionized water 1.9 Wet adhesion monomer (50% w/w) 0.8 Initiator Solution 1 Deionized water 1.4 Sodium persulfate 0.05 Initiator Solution 2 Deionized water 2.2 Sodium persulfate 0.05 Chaser-Oxidizing Agent t-butylperoxide 0.0 Deionized water 0.4 Chaser-Reducing agent Bruggolite ® FF6M 0.0 Deionized water 0.4 Total 100.0 The polymer had 52.3% solids.

Example 29 Gel Fraction and Swelling Ratio

Samples of latex polymers made in accordance with Examples 2, 3 and 5 were dried at ambient conditions in aluminum dishes for 2 weeks. Counterpart samples of polymers made in accordance with Examples 2, 3 and 5 but to which were also added an aqueous ADPH dispersion (41% w/w), were likewise then dried. The weight ratio of polymer to ADPH dispersion was 100 to 4 on wet samples. The dried films were cut to a certain weight (W1) at about 0.2 grams, and were immersed in tetrahydrofuran for three days. The insoluble portions of the polymers were separated from the rest of the solutions, and were measured to obtain their weights (W2). The gels were dried in an oven at 110° C. for three hours and their dried gel weights (W3) were measured.

The percentage of gel fraction is determined by the weight of dried gel (W3) divided by the weight of the sample (W1):

Gel Fraction % (w/w)=W3/W1

The swelling ratio is ratio of the weight of swelling gel (W2) to the weight of dried gel (W3). The observed values are set forth in following Table 13.

TABLE 13 Gel fraction and swelling ratio of self-crosslinking vinyl acrylic polymers Mw Gel Fraction Swelling Polymer (g/mole) % (w/w) Ratio Example 24 (5% AAEM) 67,000 75.1 12.4 Example 24 + ADPH dispersion 71.9 9.9 Example 25 (5% DAAM) 133,000 58.8 33.0 Example 25 + ADPH dispersion 93.6 6.0 Example 27 (2.5% DAAM) 124,000 56.4 33.1 Example 27 + ADPH dispersion 91.0 8.1 Example 28 (comparative) 304,000 44.8 47.0 The weight average of molecular weight, Mw, was determined by gas permeation chromatography.

Example 30 Semigloss Paints Made with Self-Crosslinking Vinyl Acrylic Polymers

Paint formulations with self-crosslinking vinyl acrylic polymers, and having components as described in Table 14 below, were prepared.

Paints A and B were made utilizing polymers formulated in accordance with Examples 23 and 24, respectively. Both contained self-crosslinkable functionality on polymer chains, and an aqueous adipic acid di(2-propylidene hydrazide) dispersion to cross-link polymers during and after drying of paints.

Paint C was made utilizing polymer formulated in accordance with Example 24 having the self-cross-linkable functionality AAEM. Paint C did not contain adipic acid di(2-propylidene hydrazide), and did not undergo crosslinking during and after paint drying.

Paint D was made utilizing polymer formulated in accordance with Example 28, which did not contain self-cross-linking functionality.

TABLE 14 Semigloss paint formulae Add ingredients in order: A B C D WATER 130 lb 130 lb 130 lb 130 lb Cellulosic thickener 1 1 1 1 PRESERVATIVE 2 2 2 2 TAMOL 731A 9.2 9.2 9.2 9.2 (dispersant) Titanium dioxide 245 245 245 245 Deformer 1 1 1 1 Grind for 10 minutes, then add Non-ionic surfactant 4.4 4.4 4.4 4.4 Anionic surfactant (60% w/w) 1 1 1 1 Coalescent solvents 17.5 17.5 17.5 17.5 Water 14 14 14 14 Polymer of Example 1 485.6 Polymer of Example 2 485.6 Polymer of Example 2 485.6 (comparative) Polymer of Example 6 485.6 (comparative) AMMONIA 26 BE 3.2 3.2 3.2 3.2 ROPAQUE OP-96 82.3 82.3 82.3 82.3 Aqueous ADPH 16 16 0 0 dispersion 41% w/w ACRYSOL RM-5000 6.5 6.5 6.5 6.5 WATER 16 16 16 16 NATROSOL PLUS 330 2 2 2 2 WATER 2 2 2 2 WATER 14.6 14.6 30.5 30.5 FOAMSTAR A-45 3.5 3.5 3.5 3.5 Total (gallon) 100 100 100 100

Example 31 Evaluation of Paints Made with Self-Crosslinking Vinyl Acrylic Copolymers

The results of evaluating the paints formulated in accordance with Example 30 are set forth in following Table 15.

Note that a commercial premium semi-gloss with all acrylic copolymer, Paint D, was included in the evaluation for comparison purposes. All acrylic polymers are high cost polymers and are believed to have superior performance in water and scrub resistance.

Block resistance testing was performed with a modified ASTM D4946 method. For each paint evaluated, a paint draw-down was prepared on a sealed white Leneta WK card on a vacuum plate. The draw-down was oven-dried for one day, and then dried for seven days at ambient conditions. One-inch squares were cut out of the panel and two squares were placed face-to-face. A 100-gram cubic weight was placed on top of the face-to-face squares, and that assembly was subjected in an oven to a temperature of 120° F. for 24 hours. The assembly was removed from the oven and panels were allowed to cool for one-half hour. Fusion of the squares to one another was checked by pulling them apart with a slow and steady force. Ratings of the blocking resistance indicated by that exercise is characterized in Table 5 according to the scale

5—no tack,

4—slight tack,

3—moderate tack,

2—poor tack,

1—severe tack,

0—transfer,

with additional notation of the % of film removed.

Water resistance testing was done on a 3-mil bird bar. For each paint evaluated, a paint draw-down was prepared as described for block-resistance testing. The draw-down was dried in an oven for one day and then for seven days at ambient conditions. A few drops of water were placed on the paint surface of the draw-down. After one minute, the water was then removed with a paper tower, and the wetted paint surface was scratched with a finger nail to check the hardness. A rating of 1 to 5 was given with 1 being the softest, indicating the worst water resistance, and 5 being the hardest, indicating the best water resistance.

Scrub testing was performed using ASTM D2486 Method B on a 7-mil paint draw-down dried for seven days. A BYK-Gardner Abrasion Tester with a boat weighing 1000 grams was used for the test. The scrub cycle number at failure was recorded (i.e., where the paint film was removed and the surface of the underlying substrate showed through). A higher cycle number indicates a better scrub resistance for the paint. Scrub testing was stopped at 2000 cycles even if the paint film still had not yet failed. A paint with a 2000 scrub cycle rating pursuant to the ASTM D2486 method is considered to have excellent scrubability.

Scrub testing was performed on fresh made paints, and also on paints aged for one month for the purpose of checking stability.

TABLE 15 Evaluation of paints with self-crosslinking vinyl acrylic copolymers Block Water Scrub (1 Resistance: Resistance: Scrub month aged Paint Description 1 day/7 day 1 day/7 day (cycles) paints) Example Vinyl acetate/butyl acrylic 10% 4 1.5 3 1864   2000+ 30A polymer with 3.5% DAAM Example Vinyl acetate/butyl acrylic 5 5 1.5 4 2000+ 2000+ 30B polymer with 5% AAEM Example Vinyl acetate/butyl acrylic 5 5 1 2 146 130 30C polymer with 5% AAEM, no ADPH in paint Example Vinyl acetate/butyl acrylic 40% 10% 1.5 1.5 1033   1117   30D polymer Commercial premium semigloss paint 35% 4 3 3 878 with all acrylic polymer (comparative)

Example 32 Semigloss Paints with ADPH Added at Difference Stages

The formulation of a range of paints is detailed in the following Table 16.

Paint A was made utilizing a polymer formulated in accordance with Example 24 and an ADPH dispersion was added to the paint.

Paint B was a comparative example made utilizing a polymer formulated in accordance with Example 25, which contained 5% DAAM. There was no addition of ADPH dispersion to the paint.

Paint C was made utilizing a polymer formulated in accordance with Example 26 containing 5% DAAM with ADPH dispersion added to the polymer when the polymerization was complete.

Paint D was made utilizing a polymer formulated in accordance with Example 25 with acetone and adipic acid dihydrazide added to the paint. Acetone and adipic acid dihydrazide form adipic acid di(2-propylidene hydrazide) in paint.

Paint E was made utilizing a polymer formulated in accordance with Example 27 which contained 2.5% DAAM.

Paint F was a comparative example made utilizing a polymer formulated in accordance with Example 27 and without addition of ADPH dispersion to the paint.

Paint G was a comparative example made utilizing a polymer formulated in accordance with Example 28 and having no cross-linkable functionality.

TABLE 16 Paint Formulations. Add ingredients in order: A B C D E F G WATER 64.8  64.8 64.8  64.8  64.8  64.8 64.8 PROPYLENE GLYCOL 15   15 15   15   15   15 15 NUOSEPT 95 1.6 1.6 1.6 1.6 1.6 1.6 1.6 TAMOL 1124 (dispersant) 11   11 11   11   11   11 11 Non-ionic surfactant 12.2  12.2 12.2  12.2  12.2  12.2 12.2 Titanium dioxide 295    295 295    295    295    295 295 Deformer 1 1   1 1   1   1   1 1 Anionic surfactant (60% 3   3 3   3   3   3 3 w/w) METHYL CARBITOL 15   15 15   15   15   15 15 Coalescent solvent 9.6 9.6 9.6 9.6 9.6 9.6 9.6 Polymer of Example 2 (5% 400    AAEM) Polymer of Example 3 (5% 400 400    DAAM) Polymer of Example 4 416    (5% DAAM + ADPH) Polymer of Example 5 400    400 (2.5% DAAM) Polymer of Example 6 400 Aqueous ADPH dispersion 16   0 16   0   16   0 0 41% w/w Acetone 0   0 0   3.2 0   0 0 Adipic acid dihydrazide 0   0 0   4.8 0   0 0 AMMONIA 26 BE 2.6 2.6 2.6 2.6 2.6 2.6 2.6 Open Time Additive 15   15 15   15   15   15 15 Deformer 1 1.6 1.6 1.6 1.6 1.6 1.6 1.6 HUER Thickener (High 7   7 7   7   7   7 7 Shear) HUER Thickener (Low 7.4 7.4 7.4 7.4 7.4 7.4 7.4 Shear) WATER 132.2  132.2 132.2  132.2  132.2  132.2 132.2 HUER Thickener (Middle 41   41 41   41   41   41 41 Shear) WATER 29.6  45 29.6  36   29.6  45 45 Mildewcide 2   2 2   2   2   2 2 Deformer 1 2   2 2   2   2   2 2 Deformer 2 3   3 3   3   3   3 3 Water 6.6 6.6 6.6 6.6 6.6 6.6 6.6 Total gallon 100    100 100    100    100    100 100 Scrub resistance (cycle) 2500+    1741 2500+    2500+    2500+    611 996 Block Resistance 7 Day 5   100% 5   5   5   10% 100%

Therefore, while embodiments of the invention are described with reference to exemplified embodiments, those skilled in the art will understand that variations and modifications can be effected within the scope of the invention as defined in the appended claims. Accordingly, the scope of the various embodiments of the present invention should not be limited to the above discussed embodiments, and should only be defined by the following claims and all equivalents. 

What is claimed is:
 1. A water-borne polymeric composition, which comprises water; at least one polymer formulated from one or more monomers of which at least one is a monomer that yields acetaldehyde as a hydrolysis product, and comprising one or more carbonyl groups, one or more epoxy groups, or both one or more carbonyl groups and one or more epoxy groups; and a blocked cross-linking agent having at least one hydrazone group incorporated therein.
 2. The water-borne polymeric composition of claim 1, wherein each said monomer that yields acetaldehyde is selected from the group consisting of vinyl alkyl esters.
 3. The water-borne polymeric composition of claim 2, wherein said monomer is vinyl acetate,
 4. The water-borne polymeric composition of claim 1, wherein said at least one polymer comprises different chain copolymers each with one or more reactive carbonyl groups, one or more reactive epoxy groups, or both one or more reactive carbonyl groups and one or more reactive epoxy groups, present in the composition in a range of 3% to 60% by weight.
 5. The water-borne polymeric composition of claim 1, wherein the blocked cross-linking agent comprises at least two hydrazone groups.
 6. The water-borne polymeric composition of claim 1, wherein the blocked cross-linking agent further comprises a hydrazine group.
 7. The water-borne polymeric composition of claim 1, wherein the pH of the composition is from 6.5 to 10.3.
 8. The water-borne polymeric composition of claim 7, wherein the pH of the composition is from 8.0 to 9.8.
 9. The water-borne polymeric composition of claim 8, wherein the pH of the composition is from 8.5 to 9.5.
 10. The water-borne polymeric composition of claim 1, which comprises at least one blocked cross-linking agent of formula:

and/or at least one blocked cross-linking agent of the formula

or wherein R is a divalent organic group or a covalent bond, and each of R1, R2, R3, and R4 is selected to be independently of the others hydrogen or an organic group.
 11. The water-borne polymeric composition of claim 10, wherein each of R1, R2, R3, and R4 is selected to be, independently of the others: C1 to C12 linear alkyl, alkenyl, or alkynyl; or a branched alkyl, alkenyl, or alkynyl having a C1 to C12 primary chain; or R1 and R2 or R3 and R4 are joined together to form a cyclic organic group or said linear or branched alkyl, alkenyl, or alkynyl being substituted with an hydroxyl, amino, phenyl, benzyl, or halogen.
 12. The water-borne polymeric composition of claim 11, wherein each of R1, R2, R3, and R4 is selected to be independently of the others methyl, ethyl, n-propyl, n-butyl, iso-butyl, tert-butyl, n-amyl, iso-amyl, n-hexyl, n-heptyl, n-octyl, iso-octyl, n-nonyl, n-decyl, n-undecyl or n-dodecyl.
 13. The water-borne polymeric composition of claim 11, wherein the cyclic group is cyclopentyl or cyclohexyl.
 14. The water-borne polymeric composition of claim 1, wherein the carbonyl is incorporated within a ketone, aldehyde, or anhydride group.
 15. The water-borne polymeric composition of claim 1, wherein the polymeric composition functions as a paint, primer, other coating, ink, or adhesive.
 16. The water-borne polymeric composition of claim 1, wherein the blocked cross-linking agent comprises two or more hydrazone groups.
 17. The water-borne polymeric composition of claim 16, wherein the blocked cross-linking agent has the following formula:

wherein R is a divalent organic group or a covalent bond and each of R1, R2, R3, and R4 is selected to be independent of the others hydrogen or an organic group.
 18. The water-borne polymeric composition of claim 17, wherein R is oxalic, malonic, succinic, glutaric, adipic or sebacic.
 19. The water-borne polymeric composition of claim 16, wherein the blocked cross-linking agent has the following formula:

wherein each of R′ and R″ is selected to be independently of the other a cyclic organic group.
 20. The water-borne polymeric composition of claim 1, wherein the blocked cross-linking agent is adipic di(2-butylidene hydrazide).
 21. A cross-linked polymeric material, which comprises a first polymer moiety and a second polymer moiety, at least one of said moieties being formulated from monomers of which at least one is a monomer that yields acetaldehyde as a hydrolysis product; and cross-linkage formed by reaction of a cross-linking agent with each of the first and second polymer moieties, which agent is derived from a blocked cross-linking agent having at least one hydrazone group incorporated therein, said cross-linkage being between a plurality of sites on the first polymer moiety and their respective corresponding sites on the second polymer moiety via a cross-linking moiety attached at one of said sites on the first polymer moiety and also at the corresponding site on the second polymer moiety; each of the sites on the first and second polymer moieties being one at which there was a carbonyl group or epoxy group prior to cross-linking.
 22. A method of preparing a water-borne composition, comprising: combining a blocked cross-linking agent comprising at least one hydrazone group and an aqueous dispersion of one or more cross-linkable polymers, wherein at least one polymer in the dispersion is formulated from one or more monomers of which at least one is a monomer that yields acetaldehyde as a hydrolysis product, and comprises one or more carbonyl groups, one or more epoxy groups, or both one or more carbonyl groups and one or more epoxy groups.
 23. A method of making a cross-linked polymeric material, which comprises combining an aqueous dispersion containing a first polymer moiety having incorporated therein one or more carbonyl groups, one or more epoxy groups, or both one or more carbonyl groups and one or more epoxy groups, and a second polymer moiety having incorporated therein one or more carbonyl groups, one or more epoxy groups, or both one or more carbonyl groups and one or more epoxy groups, at least one of said polymer moieties being formulated from one or more monomers of which at least one is a monomer that yields acetaldehyde as a hydrolysis product; and a blocked cross-linking agent having at last one hydrazone group incorporated therein.
 24. A method of coating a surface, comprising: applying an water-borne polymeric dispersion on a surface, wherein the aqueous polymeric dispersion comprises water, one or more polymers, and a blocked cross-linking agent comprising at least one hydrazone group, wherein at least one of the polymers is formulated from one or more monomers of which at least one is a monomer that yields acetaldehyde as a hydrolysis product, and comprises one or more carbonyl groups, one or more epoxy groups or a combination of one or more carbonyl groups and one or more epoxy groups.
 25. A water-borne composition, comprising: water; at least one polymer formulated from one or more monomers of which at least one is a monomer that yields acetaldehyde as a hydrolysis product, and having functionality capable of reacting with a cross-linking agent; and a blocked cross-linking agent comprising at least one functional group that is not capable of reacting with either said acetaldehyde or said functionality of the polymer but is convertible via an equilibrium reaction to an alternate functional group to provide the cross-linking agent which is capable of reacting with said functionality.
 26. The water-borne composition of claim 25, wherein the equilibrium reaction produces a byproduct and the equilibrium is shifted to the second functional group by evaporation of byproduct.
 27. A water-borne primer latex, comprising: water; one or more polymers having a number average molecular weight less than 100,000 Daltons, and a glass transition temperature less than 10° C., each of said polymers being formulated from one or more monomers of which at least one is a monomer that yields acetaldehyde as a hydrolysis product, and having one or more carbonyl groups, one or more epoxy groups, or a combination of one or more carbonyl groups and one or more epoxy groups; and a blocked cross-linking agent having at least one hydrazone group incorporated therein.
 28. The water-borne primer latex of claim 27, wherein said glass transition temperature is less than 6° C.
 29. The water-borne primer latex of claim 27, wherein said glass transition temperature is less than 4° C.
 30. The water-borne primer latex of claim 27, wherein said number average molecular weight is less than 50,000 Daltons.
 31. The water-borne primer latex of claim 27, wherein said number average molecular weight is less than 25,000 Daltons,
 32. The water-borne primer latex of claim 27, wherein each of the polymers is present in the composition in a range of 3% to 60% by weight.
 33. The water-borne primer latex of claim 27, wherein a ratio of the moles of blocked cross-linking agent and the number of reactive carbonyl and epoxy groups on the polymer chains is from 0.1:1 to 2:1.
 34. The water-borne primer latex of claim 27, wherein the blocked cross-linking agent comprises at least two hydrazone groups.
 35. The water-borne primer latex of claim 27, wherein the blocked cross-linking agent further comprises a hydrazine group.
 36. The water-borne primer latex of claim 27, wherein the pH of the composition is from 6.5 to 10.3.
 37. The water-borne primer latex of claim 27, wherein the blocked cross-linking agent is of the formula:

or a combination thereof; wherein R is a divalent organic group or a covalent bond, and each of R1, R2, R3, and R4 is selected to be independently of the others hydrogen or an organic group.
 38. The water-borne primer latex of claim 37, wherein each of R1, R2, R3, and R4 is selected to be independently of the others: C1 to C12 linear alkyl, alkenyl, or alkynyl group; a branched alkyl, alkenyl, or alkynyl group having a C1 to C12 primary chain; or R1 and R2 or R3 and R4 joined together to form a cyclic organic group or said linear or branched alkyl, alkenyl, or alkynyl group substituted with an hydroxyl, amino, phenyl, benzyl, or halogen.
 39. The water-borne primer latex of claim 38, wherein each of R1, R2, R3, and R4 is selected to be independently of the others methyl, ethyl, n-propyl, n-butyl, iso-butyl, tert-butyl, n-amyl, iso-amyl, n-hexyl, n-heptyl, n-octyl, iso-octyl, n-nonyl, n-decyl, n-undecyl or n-dodecyl.
 40. The water-borne primer latex of claim 38, wherein the cyclic group is cyclopentyl or cyclohexyl.
 41. The water-borne primer latex of claim 27, wherein the carbonyl is incorporated within ketone, aldehyde, or anhydride group.
 42. The water-borne primer latex of claim 35, wherein the blocked cross-linking agent has the following formula:

wherein R is a divalent organic group or a covalent bond and each of R1, R2, R3, and R4 is selected to be independent of the others hydrogen or an organic group.
 43. The water-borne primer latex of claim 42, wherein R is oxalic, malonic, succinic, glutaric, adipic or sebacic.
 44. The water-borne primer latex of claim 27, wherein the blocked cross-linking agent has the following formula:

wherein each of R′ and R″ is selected to be independently of the other a cyclic organic group.
 45. The water-borne primer latex of claim 27, wherein the blocked cross-linking agent is adipic di(2-butylidene hydrazide).
 46. A cross-linked polymeric material, which comprises a first polymer moiety and a second polymer moiety, at least one of said moieties being formulated from one or more monomers of which at least one is a monomer that yields acetaldehyde as a hydrolysis product; and cross-linkage formed by reaction of a cross-linking agent with each of the first and second polymer moieties, which cross-linking agent is derived from a blocked cross-linking agent having at least one functional group that is not capable of reacting with either acetaldehyde or any functionality of said first or second polymer moiety but is convertible via an equilibrium reaction to an alternative functional group to provide the cross-linking agent, said cross-linkage being between a plurality of sites on the first polymer moiety and their respective corresponding sites on the second polymer moiety via a cross-linking moiety attached at one of said sites on the first polymer moiety and also at the corresponding site on the second polymer moiety; each of the sites on the first and second polymer moieties being one at which there was a functionality capable of reacting with the cross-linking agent.
 47. A method of preparing a water-borne composition, comprising: combining an aqueous dispersion of one or more cross-linkable polymers, wherein at least one polymer in the dispersion is formulated from one or more monomers of which at least one is a monomer that yields acetaldehyde as a hydrolysis product, and has functionality capable of interacting with a cross-linking agent, and a blocked cross-linking agent that is not capable of reacting with either said acetaldehyde or said functionality but is convertible via an equilibrium reaction to said cross-linking agent.
 48. A method of making a cross-linked polymeric material, which comprises combining an aqueous dispersion of a first polymer moiety and a second polymer moiety, each of said polymer moieties comprising functionality capable of reacting with a cross-linking agent, at least one of said copolymer moieties being formulated from one or more monomers of which at least one is a monomer that yields acetaldehyde as a hydrolysis product; and a blocked cross-linking agent that is not capable of reacting with either said acetaldehyde or said functionality but is convertible via an equilibrium reaction to said cross-linking agent.
 49. A method of depositing adherent material on a surface, comprising: applying an water-borne polymeric dispersion on a surface, wherein the water-borne polymeric dispersion comprises water, one or more polymers formulated from one or more monomers of which at least one is a monomer that yields acetaldehyde as a hydrolysis product, and which include functionality capable of reacting with a cross-linking agent, and a blocked cross-linking agent that is not capable of reacting with either said acetaldehyde or said functionality but is convertible via an equilibrium reaction to said cross-linking agent.
 50. A material adherent to a surface which is formed in accordance with the method defined in claim
 49. 